KR100524248B1 - Epoxy resin composition and semiconductor device using the same - Google Patents
Epoxy resin composition and semiconductor device using the same Download PDFInfo
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- KR100524248B1 KR100524248B1 KR10-1998-0046809A KR19980046809A KR100524248B1 KR 100524248 B1 KR100524248 B1 KR 100524248B1 KR 19980046809 A KR19980046809 A KR 19980046809A KR 100524248 B1 KR100524248 B1 KR 100524248B1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
- C08G59/245—Di-epoxy compounds carbocyclic aromatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/3218—Carbocyclic compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- C08L63/04—Epoxynovolacs
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/52—Encapsulations
- H01L33/56—Materials, e.g. epoxy or silicone resin
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12528—Semiconductor component
Abstract
본 발명은 할로겐계, 삼산화안티몬 등의 난연제를 함유하지 않은, 난연성이 뛰어난 반도체 밀봉용 에폭시 수지 조성물을 제공한다. 즉, 본 발명은 (A) 분자중에 비페닐 유도체 및/또는 나프탈렌 유도체를 포함하는 노볼락 구조의 페놀 수지를 총페놀 수지량 중에 30 ∼ 100 중량 % 함유하는 페놀 수지, (B) 분자 중에 비페닐 유도체 및/또는 나프탈렌 유도체를 포함하는 노볼락 구조의 에폭시 수지를 총에폭시 수지량 중에 30 ∼ 100 중량 % 함유하는 에폭시 수지, (C) 무기 충전재, (D) 경화 촉진제를 필수 성분으로 하는 것을 특징으로 하는 반도체 밀봉용 에폭시 수지 조성물이다. This invention provides the epoxy resin composition for semiconductor sealing excellent in flame retardance which does not contain a flame retardant, such as a halogen type and antimony trioxide. That is, the present invention relates to a phenol resin containing 30 to 100% by weight of a phenolic resin having a novolac structure containing a biphenyl derivative and / or a naphthalene derivative in a molecule (A), and a biphenyl in a molecule (B). Epoxy resin containing 30-100 weight% of novolak-type epoxy resin containing a derivative and / or a naphthalene derivative in total epoxy resin weight, (C) inorganic filler, (D) hardening accelerator as essential components, It is characterized by the above-mentioned. It is an epoxy resin composition for semiconductor sealing.
Description
본 발명은 난연성 및 신뢰성이 뛰어난 반도체 밀봉용 에폭시 수지 조성물 및 이것을 사용한 반도체 장치에 관한 것이다.The present invention relates to an epoxy resin composition for semiconductor sealing excellent in flame retardancy and reliability, and a semiconductor device using the same.
종래, 다이오드, 트랜지스터, 집적회로 등의 전자 부품은 주로 에폭시 수지 조성물로 밀봉되어 있다. 이 에폭시 수지 조성물중에는 난연성을 확보하기 위하여 난연제로서 할로겐계 난연제와 삼산화안티몬이 배합되어 있다. 그런데, 환경·위생의 점에서 할로겐계 난연제, 삼산화안티몬을 사용하지 않은 난연성이 뛰어난 에폭시 수지 조성물의 개발이 요구되고 있다.Conventionally, electronic components such as diodes, transistors, and integrated circuits are mainly sealed with an epoxy resin composition. In this epoxy resin composition, a halogen type flame retardant and antimony trioxide are mix | blended as a flame retardant in order to ensure flame retardance. By the way, development of the epoxy resin composition excellent in the flame retardance which does not use a halogen type flame retardant and antimony trioxide from the point of view of environment and hygiene is calculated | required.
이 요구에 대하여 수산화알루미늄이나 수산화마그네슘 등의 수산화물, 붕소계 화합물이 검토되어 왔으나, 다량으로 배합하지 않으면 난연성의 효과가 발현되지 않고, 불순물이 많아 내습성에 문제가 있는 점에서 실용화될 수 없었다. 또한, 붉은인계 난연제는 소량의 첨가로 효과가 있어서 에폭시 수지 조성물의 난연화에 유용하나, 붉은인은 미량의 수분과 반응하여 포스핀이나 부식성 인산을 발생시키기 때문에, 내습성에 문제가 있어서 내습성에 대한 요구가 매우 엄격한 반도체 밀봉용 에폭시 수지 조성물에는 사용할 수 없다. 따라서, 붉은인 입자를 수산화알루미늄, 금속산화물, 그 외 무기화합물, 열경화성 수지 등의 유기 화합물로 피복하여 붉은인의 안정화를 도모하고 있으나, 여전히 내습성에 문제가 있고, 난연성·내습성이 양립하는, 할로겐계 난연제, 삼산화안티몬을 사용하지 않은 반도체 밀봉용 에폭시 수지 조성물이 개발되어 있지 않은 것이 실상이다.Hydrocarbons and boron-based compounds such as aluminum hydroxide and magnesium hydroxide have been studied for this requirement. However, if they are not mixed in a large amount, the effect of flame retardancy is not expressed, and they cannot be put to practical use because they have a large amount of impurities and have problems in moisture resistance. In addition, red phosphorus-based flame retardant is effective for the flame retardation of the epoxy resin composition because it is effective by adding a small amount, but red phosphorus reacts with a small amount of water to generate phosphine or corrosive phosphoric acid, which is problematic in terms of moisture resistance and moisture resistance. It cannot be used for the epoxy resin composition for semiconductor sealing which has a very severe demand for it. Therefore, red phosphorus particles are coated with organic compounds such as aluminum hydroxide, metal oxides, other inorganic compounds, and thermosetting resins to stabilize red phosphorus, but there are still problems in moisture resistance and both flame resistance and moisture resistance are compatible. It is a fact that the epoxy resin composition for semiconductor sealing which does not use the halogen type flame retardant and antimony trioxide has not been developed.
본 발명은 이와 같은 문제에 대하여 난연제를 일체 사용하지 않고, 난연성 및 신뢰성이 뛰어난 반도체 밀봉용 에폭시 수지 조성물 및 이것을 사용한 반도체 장치를 제공하는 것이다.This invention provides the epoxy resin composition for semiconductor sealing excellent in flame retardancy and reliability, and a semiconductor device using the same, without using a flame retardant at all against such a problem.
본 발명자는 상기한 과제를 해결하기 위하여 예의 연구를 거듭한 결과, 특정의 에폭시 수지와 특정의 페놀 수지를 조합하면 난연제를 사용하지 않고 난연성 및 신뢰성이 뛰어난 반도체 밀봉용 에폭시 수지 조성물이 얻어짐을 발견하였다. 또한, 반응성을 제어하면 난연성이 더욱 레벨업됨도 발견하여 본 발명을 완성하기에 이르렀다. 즉, 본 발명은 (A) 분자중에 비페닐 유도체 및/또는 나프탈렌 유도체를 포함하는 노볼락 구조의 페놀 수지를 총페놀 수지량 중에 30 ∼ 100 중량 % 함유하는 페놀 수지, (B) 분자 중에 비페닐 유도체 및/또는 나프탈렌 유도체를 포함하는 노볼락 구조의 에폭시 수지를 총에폭시 수지량 중에 30 ∼ 100 중량 % 함유하는 에폭시 수지, (C) 무기 충전재, (D) 경화 촉진제를 필수 성분으로 하는 것을 특징으로 하는 반도체 밀봉용 에폭시 수지 조성물이다. 본 발명의 반도체 밀봉용 에폭시 수지 조성물은 총에폭시 수지의 에폭시기 수에 대한 총페놀 수지의 페놀성 수산기 수의 비가 1 보다 크고 2 이하이면 더욱 바람직하다. 본 발명은 이들 수지 조성물에 의해 반도체가 밀봉되어 이루어지는 수지 밀봉형 반도체 장치도 제공한다.MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to solve the said subject, when the specific epoxy resin and the specific phenol resin were combined, it discovered that the epoxy resin composition for semiconductor sealing excellent in flame retardancy and reliability was obtained without using a flame retardant. . In addition, it has also been found that flame retardancy is further improved by controlling the reactivity, thus completing the present invention. That is, the present invention relates to a phenol resin containing 30 to 100% by weight of a phenolic resin having a novolac structure containing a biphenyl derivative and / or a naphthalene derivative in a molecule (A), and a biphenyl in a molecule (B). Epoxy resin containing 30-100 weight% of novolak-type epoxy resin containing a derivative and / or a naphthalene derivative in total epoxy resin weight, (C) inorganic filler, (D) hardening accelerator as essential components, It is characterized by the above-mentioned. It is an epoxy resin composition for semiconductor sealing. The epoxy resin composition for semiconductor encapsulation of the present invention is more preferable if the ratio of the number of phenolic hydroxyl groups of the total phenol resin to the number of epoxy groups of the total epoxy resin is greater than 1 and less than 2. The present invention also provides a resin-sealed semiconductor device in which a semiconductor is sealed by these resin compositions.
본 발명자는 에폭시 수지 조성물에 있어서, 특정의 페놀 수지와 특정의 에폭시 수지의 조합이 난연성, 신뢰성이 뛰어남을 발견하였다. 또한, 반응성을 제어함으로써 난연성이 더욱 향상됨을 발견하였다.MEANS TO SOLVE THE PROBLEM This inventor discovered that the combination of a specific phenol resin and a specific epoxy resin was excellent in flame retardancy and reliability in an epoxy resin composition. It has also been found that flame retardancy is further improved by controlling reactivity.
본 발명의 특정의 페놀 수지란 분자중에 비페닐 유도체 및/또는 나프탈렌 유도체를 포함하는 노볼락 구조의 페놀 수지이고, 특정의 에폭시 수지란 분자 중에 비페닐 유도체 및/또는 나프탈렌 유도체를 포함하는 노볼락 구조의 에폭시 수지이고, 이들은 각각 페놀 수지 및 에폭시 수지의 분자중에 비페닐 유도체 및/또는 나프탈렌 유도체의 방향족 고리를 함유하는 것이다.The specific phenol resin of the present invention is a phenol resin having a novolak structure containing a biphenyl derivative and / or a naphthalene derivative in a molecule, and the specific epoxy resin is a novolak structure containing a biphenyl derivative and / or a naphthalene derivative in a molecule. And epoxy resins, which contain aromatic rings of biphenyl derivatives and / or naphthalene derivatives in the molecules of the phenol resin and the epoxy resin, respectively.
페놀 수지 또는 에폭시 수지에 비페닐 유도체나 나프탈렌 유도체와 같은 방향족환이 포함되면 분자간의 결합에너지가 커져서 연소에 의한 분해가 잘 일어나지 않고 난연성이 발현된다. 페놀 수지 혹은 에폭시 수지의 분자중에 존재하는 방향족환 수는 많은 편, 즉 나프탈렌보다 안트라센 편이 잘 타지 않게 되어 난연성은 향상되지만, 연화점이 너무 높아져서 유동성이 나빠지므로, 비페닐 유도체 및 나프탈렌 유도체가 난연성과 유동성의 밸런스가 좋아서 가장 적합하다.When an aromatic ring such as a biphenyl derivative or a naphthalene derivative is included in the phenol resin or the epoxy resin, the binding energy between molecules increases, so that decomposition by combustion does not occur easily, and flame retardancy is expressed. The number of aromatic rings in the molecule of phenol resin or epoxy resin is high, that is, the anthracene side is less burned than naphthalene, so that the flame retardancy is improved. However, the softening point becomes too high and the fluidity is poor. Therefore, the biphenyl derivative and the naphthalene derivative are flame retardant and fluid. Good balance of the best.
또한, 반응성을 제어함으로써 난연성을 더욱 향상시킬 수 있다. 즉, 총에폭시 수지의 에폭시기 수에 대한 총페놀 수지의 페놀성 수산기 수의 비를 1 보다 크게 하면 난연성이 더욱 향상된다. 이것은 수지 조성물 중에 에폭시기와 반응하지 않고 남은 수산기가 존재하고 있으며, 수지 조성물의 경화물을 연소시킬 때, 잔여 수산기끼리의 탈수 열분해에 의한 흡열반응이 일어나기 때문일 것이다. 총에폭시 수지의 에폭시기 수에 대한 총페놀 수지의 페놀성 수산기 수의 비는 2 이하가 바람직하며, 2 를 넘으면 반응성이 극단적으로 저하된다. 더욱 바람직하게는 이 비는 1.1 이상, 1.5 이하이다.In addition, the flame retardancy can be further improved by controlling the reactivity. That is, when the ratio of the number of phenolic hydroxyl groups of the total phenol resin to the number of epoxy groups of the total epoxy resin is larger than 1, the flame retardancy is further improved. This may be because a hydroxyl group remaining without reacting with an epoxy group exists in the resin composition, and when the cured product of the resin composition is burned, an endothermic reaction by dehydration pyrolysis of the remaining hydroxyl groups occurs. The ratio of the number of phenolic hydroxyl groups of the total phenol resin to the number of epoxy groups of the total epoxy resin is preferably 2 or less, and when it exceeds 2, the reactivity extremely decreases. More preferably, this ratio is 1.1 or more and 1.5 or less.
범용 페놀 수지 (페놀노볼락) 와 에폭시 수지 (오르토크레졸노볼락형 에폭시) 의 조합에서는, 총 에폭시 수지의 에폭시기 수에 대하여 총페놀 수지의 페놀성 수산기 수의 비를 크게하면 흡수율이 커져서 내습신뢰성은 저하되는 경향이 있다. 그러나, 본 발명의 특정의 페놀 수지와 에폭시 수지의 조합에 있어서는, 흡수율의 대폭적인 증가는 보이지 않으며 내습신뢰성의 저하도 인정되지 않는다. 이는 본 발명의 특정의 페놀 수지 및 에폭시 수지가 소수성 방향족 고리를 가지고 있고, 가교분자간 거리가 범용 페놀 수지 (페놀노볼락) 와 에폭시 수지 (오르토크레졸노볼락형 에폭시) 와 비교하여 크기 때문에 흡수율의 대폭적인 증가가 인정되지 않는다고 생각된다.In the combination of a general-purpose phenol resin (phenol novolac) and an epoxy resin (orthocresol novolac-type epoxy), when the ratio of the number of phenolic hydroxyl groups of the total phenolic resin to the number of epoxy groups of the total epoxy resin is increased, the water absorption becomes high and It tends to be lowered. However, in the combination of the specific phenol resin and epoxy resin of this invention, a significant increase in water absorption is not seen, and the fall of moisture-reliability is also not recognized. This is because the specific phenol resin and the epoxy resin of the present invention have a hydrophobic aromatic ring, and the distance between the crosslinking molecules is large compared with the general phenol resin (phenol novolac) and the epoxy resin (orthocresol novolac type epoxy) It is thought that no increase is recognized.
본 발명의 특정의 페놀 수지란 분자중에 비페닐 유도체 및/또는 나프탈렌 유도체를 포함하는 노볼락 구조의 페놀 수지이고, 구체적으로 비페닐 유도체를 포함하는 노볼락 구조의 페놀 수지는 화학식 1 로 표시된다.The specific phenol resin of the present invention is a phenol resin having a novolak structure containing a biphenyl derivative and / or a naphthalene derivative in a molecule, and specifically, a phenol resin having a novolak structure containing a biphenyl derivative is represented by the formula (1).
화학식 1 로 표시되는 페놀 수지는 페놀과, 예를 들면 비스메톡시메틸렌비페닐을 반응시켜 얻어지는 수지이다. 화학식 1 의 n 은 1 ∼ 10 이고, n 이 11 이상이 되면, 수지점도가 너무 높아져서 유동성이 저하된다. 난연성을 발현시키기 위해서는 화학식 1 로 표시되는 페놀 수지를 총페놀 수지량 중에 30 중량 % 이상, 바람직하게는 50 중량 % 이상 배합하는 것이 바람직하다. 30 중량 % 미만이면 난연성이 불충분하다.The phenol resin represented by General formula (1) is resin obtained by making phenol react with bismethoxymethylene biphenyl, for example. When n is 1-10, and n becomes 11 or more, resin viscosity will become high too much and fluidity will fall. In order to express flame retardancy, it is preferable to mix | blend a phenol resin represented by General formula (1) in 30 weight% or more, Preferably 50 weight% or more in total phenol resin amount. Less than 30% by weight is insufficient in flame retardancy.
구체적인 나프탈렌 유도체를 포함하는 노볼락 구조의 페놀 수지는 화학식 3 및 화학식 4 로 표시되고, 각각 α-나프톨 및 β-나프톨을 베이스로 하고 있다.The phenol resin of the novolak structure containing a specific naphthalene derivative is represented by General formula (3) and general formula (4), and is based on (alpha)-naphthol and (beta) -naphthol, respectively.
화학식 3 의 n 은 1 ∼ 7 이고, n 이 8 이상이 되면, 수지점도가 너무 높아져서 유동성이 저하된다. 난연성을 발현시키기 위해서는 화학식 3 으로 표시되는 페놀 수지를 총페놀 수지량 중에 30 중량 % 이상, 바람직하게는 50 중량 % 이상 배합하는 것이 바람직하다. 30 중량 % 미만이면 난연성이 불충분하다. 화학식 4 의 n 은 1 ∼ 10 이고, n 이 11 이상이 되면 수지점도가 너무 높아져서 유동성이 저하된다. 난연성을 발현시키기 위해서는 화학식 4 로 표시되는 페놀 수지를 총페놀 수지량 중에 30 중량 % 이상, 바람직하게는 50 중량 % 이상 배합하는 것이 바람직하다. 30 중량 % 미만이면 난연성이 불충분하다.N in the formula (3) is 1 to 7, when n is 8 or more, the resin viscosity becomes too high, the fluidity is lowered. In order to express flame retardance, it is preferable to mix | blend 30 weight% or more, Preferably it is 50 weight% or more in the phenol resin represented by General formula (3) in total phenol resin amount. Less than 30% by weight is insufficient in flame retardancy. N in the formula (4) is 1 to 10, when n is 11 or more, the resin viscosity is too high, the fluidity is lowered. In order to express flame retardancy, it is preferable to mix | blend 30 weight% or more, Preferably it is 50 weight% or more in the phenol resin represented by General formula (4) in total phenol resin amount. Less than 30% by weight is insufficient in flame retardancy.
본 발명에서는 특정의 페놀 수지 이외에 다른 페놀 수지를 병용할 수 있다. 다른 페놀 수지로서는, 1 분자중에 2 개 이상의 페놀성 수산기를 갖는 것, 예를 들면 페놀노볼락수지, 크레졸노볼락수지, 디시클로펜타디엔 변성페놀 수지, 크실릴렌 변성페놀 수지, 테르펜 변성페놀 수지, 트리페놀메탄형 노볼락수지 등을 들 수 있다.In this invention, other phenol resin can be used together in addition to specific phenol resin. As another phenol resin, what has two or more phenolic hydroxyl groups in 1 molecule, for example, a phenol novolak resin, a cresol novolak resin, a dicyclopentadiene modified phenol resin, a xylylene modified phenol resin, a terpene modified phenol resin And triphenolmethane type novolak resins.
본 발명의 특정의 에폭시 수지란 분자중에 비페닐 유도체 및/또는 나프탈렌 유도체를 포함하는 노볼락 구조의 에폭시 수지이고, 구체적으로 비페닐 유도체를 포함하는 노볼락 구조의 에폭시 수지는 화학식 1 의 페놀 수지를 글리시딜에테르화시켜 얻어지며, 화학식 2 로 표시된다.Specific epoxy resin of the present invention is a novolak-type epoxy resin containing a biphenyl derivative and / or naphthalene derivative in the molecule, specifically, a novolak-type epoxy resin containing a biphenyl derivative is a phenol resin of formula (1) Obtained by glycidyl ether, it is represented by the formula (2).
화학식 2 의 n 은 1 ∼ 10 이고, n 이 11 이상이 되면, 수지점도가 너무 높아져서 유동성이 저하된다. 난연성을 발현시키기 위해서는 화학식 2 로 표시되는 에폭시 수지를 총에폭시 수지중에 30 중량 % 이상, 바람직하게는 50 중량 % 이상 배합하는 것이 바람직하다. 30 중량 % 미만이면 난연성이 불충분하다.When n is 1-10, and n becomes 11 or more, resin viscosity will become high too much and fluidity will fall. In order to express flame retardancy, it is preferable to mix | blend the epoxy resin represented by General formula (2) in 30 weight% or more, Preferably 50 weight% or more in total epoxy resin. Less than 30% by weight is insufficient in flame retardancy.
구체적인 나프탈렌 유도체를 포함하는 노볼락 구조의 에폭시 수지는 화학식 3 및 화학식 4 각각의 페놀 수지를 글리시딜에테르화시켜 얻어지며, 화학식 5 및 화학식 6 으로 표시된다.The novolac epoxy resin containing a specific naphthalene derivative is obtained by glycidyl etherification of each of the phenol resins of the formulas (3) and (4), and is represented by the formulas (5) and (6).
화학식 5 의 n 은 1 ∼ 7 이고, n 이 8 이상이 되면, 수지점도가 너무 높아져서 유동성이 저하된다. 난연성을 발현시키기 위해서는 화학식 5 로 표시되는 에폭시 수지를 총에폭시 수지량 중에 30 중량 % 이상, 바람직하게는 50 중량 % 이상 배합하는 것이 바람직하다. 30 중량 % 미만이면 난연성이 불충분하다. 화학식 6 의 n 은 1 ∼ 10 이고, n 이 11 이상이 되면, 수지점도가 너무 높아져서 유동성이 저하된다. 난연성을 발현시키기 위해서는 화학식 6 으로 표시되는 에폭시 수지를 총에폭시 수지량 중에 30 중량 % 이상, 바람직하게는 50 중량 % 이상 배합하는 것이 바람직하다. 30 중량 % 미만이면 난연성이 불충분하다.N in the formula (5) is 1 to 7, when n is 8 or more, the resin viscosity is too high, the fluidity is lowered. In order to express flame retardancy, it is preferable to mix | blend the epoxy resin represented by General formula (5) in 30 weight% or more, Preferably 50 weight% or more in total epoxy resin amount. Less than 30% by weight is insufficient in flame retardancy. When n is 1-10, and n becomes 11 or more, resin viscosity will become high too much and fluidity will fall. In order to express flame retardance, it is preferable to mix | blend the epoxy resin represented by General formula (6) in 30 weight% or more, Preferably 50 weight% or more in total epoxy resin amount. Less than 30% by weight is insufficient in flame retardancy.
본 발명에서는 특정의 에폭시 수지 이외에 다른 에폭시 수지를 병용할 수 있다. 다른 에폭시 수지로서는 1 분자중에 에폭시기를 2 개 이상 갖는 것, 예를 들면 비페닐형 에폭시 수지, 히드로퀴논형 에폭시 수지, 스틸벤형 에폭시 수지, 비스페놀형 에폭시 수지, 페놀노볼락형 에폭시 수지, 크레졸노볼락형 에폭시 수지, 트리페놀메탄형 에폭시 수지, 알킬변성트리페놀메탄형 에폭시 수지, 트리아진핵 함유 에폭시 수지, 디시클로펜타디엔 변성페놀형 에폭시 수지 등을 들 수 있다.In the present invention, other epoxy resins may be used in addition to the specific epoxy resins. As another epoxy resin, what has two or more epoxy groups in 1 molecule, for example, a biphenyl type epoxy resin, a hydroquinone type epoxy resin, a stilbene type epoxy resin, a bisphenol type epoxy resin, a phenol novolak type epoxy resin, a cresol novolak type Epoxy resin, a triphenol methane type epoxy resin, an alkyl modified triphenol methane type epoxy resin, a triazine nucleus containing epoxy resin, a dicyclopentadiene modified phenol type epoxy resin, etc. are mentioned.
본 발명에 사용하는 경화 촉진제로서는, 에폭시기와 페놀성 수산기의 경화반응을 촉진시키는 것이면 되며, 일반적으로 밀봉 재료에 사용되는 것을 널리 사용할 수 있다. 예를 들면, 1,8-디아자비시클로(5,4,0)운데센-7, 트리페닐포스핀, 2-메틸이미다졸 등을 들 수 있고, 이들은 단독이나 혼합하여 사용해도 무방하다.As a hardening accelerator used for this invention, what is necessary is just to accelerate hardening reaction of an epoxy group and a phenolic hydroxyl group, and what is generally used for a sealing material can be used widely. For example, 1, 8- diazabicyclo (5, 4, 0) undecene-7, triphenyl phosphine, 2-methylimidazole, etc. are mentioned, These may be used individually or in mixture.
본 발명에 사용하는 무기 충전재로서는, 일반적으로 밀봉 재료에 사용되는 것을 널리 사용할 수 있으며, 예를 들면 용융실리카 분말, 결정실리카 분말, 알루미나, 질화규소 등을 들 수 있고, 이들은 단독이나 혼합하여 사용해도 무방하다. 이들 무기 충전재의 배합량으로서는 성형성과 난연성의 밸런스에서 전수지 조성물 중에 70 ∼ 95 중량 % 함유시키는 것이 바람직하다. 70 중량 % 미만이면 난연성이 감소할 것이고, 95 중량 % 를 넘으면 성형성의 문제가 발생하여 바람직하지 못하다.As an inorganic filler used for this invention, what is generally used for a sealing material can be used widely, For example, melted silica powder, crystalline silica powder, alumina, silicon nitride, etc. are mentioned, These may be used individually or in mixture. Do. As a compounding quantity of these inorganic fillers, it is preferable to contain 70 to 95 weight% in a resin composition in balance of moldability and flame retardance. If it is less than 70% by weight, the flame retardancy will decrease, and if it exceeds 95% by weight, a problem of formability occurs, which is not preferable.
본 발명의 수지 조성물은 (A) ∼ (D) 성분 외에 필요에 따라 카본블랙 등의 착색제, γ-글리시독시프로필트리메톡시실란 등의 커플링제, 실리콘오일, 실리콘고무 등의 저응력성분, 천연왁스, 합성왁스, 고급 지방산 및 그 금속염류 혹은 파라핀 등의 이형제, 산화방지제 등의 각종 첨가제를 적절히 배합해도 무방하다.The resin composition of the present invention may contain, if necessary, a coloring agent such as carbon black, a coupling agent such as γ-glycidoxypropyltrimethoxysilane, low stress components such as silicone oil and silicone rubber, Various additives, such as a natural wax, a synthetic wax, a higher fatty acid, its metal salt, or a mold release agent, such as a paraffin, and antioxidant, may be mix | blended suitably.
본 발명의 수지 조성물은, (A) ∼ (D) 성분 및 그 외의 첨가제 등을 믹서를 사용해서 상온혼합하여 롤, 압출기 등의 혼합반죽기로 혼합반죽하고, 냉각후 분쇄하여 얻어진다.The resin composition of this invention is obtained by mixing (A)-(D) component, other additives, etc. at room temperature using a mixer, mixing and kneading with mixing dough, such as a roll and an extruder, and after grinding, grinding | pulverizing.
본 발명의 수지 조성물을 사용해서 반도체 등의 전자 부품을 밀봉하여 수지밀봉형 반도체장치를 제조하기 위해서는, 트랜스퍼(transfer) 성형, 압축 성형, 사출 성형 등, 종래부터의 공지의 수법으로 성형경화하면 된다.In order to manufacture a resin sealing semiconductor device by sealing electronic components, such as a semiconductor, using the resin composition of this invention, what is necessary is just to harden shape | molding by conventionally well-known methods, such as transfer molding, compression molding, injection molding, and the like. .
이들 수지 조성물은 전기부품 혹은 전자 부품인 트랜지스터, 집적회로 등의 피복, 절연, 밀봉 등에 적용할 수 있다.These resin compositions can be applied to coating, insulation and sealing of transistors, integrated circuits and the like which are electrical components or electronic components.
또한, 전기부품, 전자 부품 이외의 통상의 성형품에도 유효하며 적용할 수 있다.Moreover, it is effective and applicable also to normal molded articles other than an electrical component and an electronic component.
이하, 본 발명의 실시예를 나타내는데, 본 발명은 이들에 한정되는 것은 아니다.Hereinafter, although the Example of this invention is shown, this invention is not limited to these.
실시예 및 비교예에서 사용한 에폭시 수지 및 페놀 수지의 번호 및 구조를 정리하여 다음에 나타낸다.The numbers and structures of the epoxy resins and phenol resins used in Examples and Comparative Examples are collectively shown below.
·페놀 수지 1 : 화학식 1 로 표시되는 페놀 수지 (수산기당량 199 g/eq)Phenolic resin 1: Phenolic resin represented by the formula (1) (hydroxyl equivalent 199 g / eq)
[화학식 1][Formula 1]
·페놀 수지 2 : 화학식 3 으로 표시되는 페놀 수지 (수산기당량 210 g/eq)Phenolic resin 2: Phenolic resin represented by the formula (3) (hydroxy group equivalent 210 g / eq)
[화학식 3][Formula 3]
·페놀 수지 3 : 화학식 4 로 표시되는 페놀 수지 (수산기당량 210 g/eq)Phenolic resin 3: Phenolic resin represented by the formula (4) (hydroxy group equivalent 210 g / eq)
[화학식 4][Formula 4]
·페놀 수지 4 : 화학식 7 로 표시되는 페놀 수지 (수산기당량 175 g/eq)Phenolic resin 4: Phenolic resin represented by the formula (7) (hydroxyl equivalent 175 g / eq)
[화학식 7][Formula 7]
·페놀 수지 5 : 화학식 8 로 표시되는 페놀 수지 (수산기당량 97 g/eq)Phenolic resin 5: Phenolic resin represented by the formula (8) (hydroxy group equivalent 97 g / eq)
[화학식 8][Formula 8]
·에폭시 수지 1 : 화학식 2 로 표시되는 구조를 주성분으로 하는 에폭시 수지 (에폭시 당량 274 g/eq)Epoxy Resin 1: Epoxy resin having a structure represented by the formula (2) as a main component (epoxy equivalent 274 g / eq)
[화학식 2][Formula 2]
·에폭시 수지 2 : 화학식 5 로 표시되는 구조를 주성분으로 하는 에폭시 수지 (에폭시 당량 270 g/eq)Epoxy resin 2: Epoxy resin having a structure represented by the formula (5) as a main component (epoxy equivalent 270 g / eq)
[화학식 5][Formula 5]
·에폭시 수지 3 : 화학식 6 으로 표시되는 구조를 주성분으로 하는 에폭시 수지 (에폭시 당량 270 g/eq)Epoxy Resin 3: Epoxy resin having a structure represented by the formula (6) as a main component (epoxy equivalent 270 g / eq)
[화학식 6][Formula 6]
·에폭시 수지 4 : 화학식 9 로 표시되는 구조를 주성분으로 하는 에폭시 수지 (에폭시 당량 190 g/eq)Epoxy resin 4: Epoxy resin having a structure represented by the formula (9) as a main component (epoxy equivalent 190 g / eq)
·에폭시 수지 5 : 화학식 10 의 4,4'-비스(2,3-에폭시프로폭시)-3,3',5,5'-테트라메틸스틸벤을 주성분으로 하는 수지 60 중량 % 와 화학식 11 의 4,4'-비스(2,3-에폭시프로폭시)-5-tert-부틸-2,3',5'-트리메틸스틸벤을 주성분으로 하는 수지 40 중량 % 의 혼합물 (에폭시 당량 210 g/eq)Epoxy Resin 5: 60% by weight of a resin mainly composed of 4,4'-bis (2,3-epoxypropoxy) -3,3 ', 5,5'-tetramethylstilbene of Formula 10 and Formula 11 A mixture of 40% by weight of a resin based on 4,4'-bis (2,3-epoxypropoxy) -5-tert-butyl-2,3 ', 5'-trimethylstilbene (epoxy equivalent 210 g / eq )
·에폭시 수지 6 : 화학식 12 로 표시되는 구조를 주성분으로 하는 에폭시 수지 (에폭시 당량 196 g/eq)Epoxy resin 6: Epoxy resin mainly containing a structure represented by general formula (12) (epoxy equivalent 196 g / eq)
·에폭시 수지 7 : 화학식 13 으로 표시되는 구조를 주성분으로 하는 에폭시 수지 (에폭시 당량 171 g/eq)Epoxy resin 7: Epoxy resin having a structure represented by the formula (13) as a main component (epoxy equivalent 171 g / eq)
그리고, 실시예 11, 14, 비교예 1 ∼ 3, 5 ∼ 7 에 사용하는 페놀노볼락수지의 수산기 당량은 104 g/eq, 실시예 9, 11, 비교예 1 ∼ 3, 5 ∼ 7 에 사용하는 오르토크레졸노볼락형 에폭시 수지의 에폭시 당량은 200 g/eq 이다. 실시예 4 ∼ 15, 비교예 5 ∼ 7 에 사용하는 용융구상 실리카의 평균입경은 22 ㎛, 비표면적은 5.0 ㎡/g 이다.And the hydroxyl equivalent of the phenol novolak resin used for Examples 11 and 14 and Comparative Examples 1-3 and 5-7 is used for 104 g / eq, Examples 9 and 11, and Comparative Examples 1-3 and 5-7. The epoxy equivalent of the orthocresol novolak-type epoxy resin to be 200 g / eq. The average particle diameter of the molten spherical silica used for Examples 4-15 and Comparative Examples 5-7 is 22 micrometers, and specific surface area is 5.0 m <2> / g.
실시예 1Example 1
·페놀 수지 1 123 중량부Phenolic resin 1 123 parts by weight
·에폭시 수지 1 170 중량부Epoxy resin 1 170 parts by weight
(페놀성 수산기의 수와 에폭시기 수의 비 1.0)(Ratio 1.0 of the number of phenolic hydroxyl groups and the number of epoxy groups)
·용융파쇄실리카(평균입경 15 ㎛, 비표면적 2.2 ㎡/g) 700 중량부700 parts by weight of molten crushed silica (average particle size 15 탆, specific surface area 2.2 m 2 / g)
·트리페닐포스핀 2 중량부Triphenylphosphine 2 parts by weight
·카본블랙 2 중량부Carbon black 2 parts by weight
·카르나바왁스 3 중량부Carnava wax 3 parts by weight
를 상온에서 슈퍼믹서를 사용해서 혼합하여 70 ∼ 100 ℃ 에서 롤혼합반죽하고, 냉각후 분쇄하여 수지 조성물로 한다. 얻어진 수지 조성물을 타블렛화하고, 저압트랜스퍼 성형기로 175 ℃, 70 ㎏/㎠, 120 초의 성형조건에서 난연성시험용 시험편을 제작한다. 또한, 내습시험용으로서 3.0 × 3.5 ㎜ 의 반도체 팁을 탑재한 16 pDIP 를 상기 타블렛화한 에폭시 수지 조성물을 사용해서 밀봉한다. 하기 난연성시험, 내습성시험을 실시한다. 평가결과를 표 1 에 나타낸다.The mixture was mixed at room temperature using a supermixer, roll-mixed at 70 to 100 ° C., cooled and pulverized to obtain a resin composition. The obtained resin composition is tableted, and the test piece for flame-retardance test is produced on the molding conditions of 175 degreeC, 70 kg / cm <2>, and 120 second with a low pressure transfer molding machine. In addition, 16 pDIP equipped with a 3.0 x 3.5 mm semiconductor tip for moisture resistance test is sealed using the tableted epoxy resin composition. The following flame resistance test and moisture resistance test are carried out. Table 1 shows the results of the evaluation.
난연성시험 : UL-94 수직시험 (시료두께 1.6 ㎜)Flame retardancy test: UL-94 vertical test (sample thickness 1.6 ㎜)
난연성 (V-0) 의 판정 : Fmax 10 초 이내Determination of flame retardancy (V-0): Fmax within 10 seconds
ΣF 50 초 이내ΣF within 50 seconds
단, ΣF : 플레이밍시간의 합계 (초)However, ΣF: sum of flaming times (seconds)
Fmax : 플레이밍시간의 최대치 (초)Fmax: Maximum flaming time in seconds
내습성시험 : 밀봉한 테스트용 반도체에 프레셔쿠커시험 (125 ℃, 100 RH%) 을 실행하여 회로의 오픈불량을 측정한다. 내습성을 프레셔쿠커시험에서의 불량발생시간 (hr) 으로 나타낸다.Moisture resistance test: A pressure cooker test (125 ° C, 100 RH%) is performed on the sealed test semiconductor to measure the open defect of the circuit. Moisture resistance is indicated by the failure occurrence time (hr) in the pressure cooker test.
실시예 2 ∼ 15, 비교예 1 ∼ 7Examples 2-15, Comparative Examples 1-7
표 1, 표 2 및 표 3 의 배합에 따라 실시예 1 과 동일한 방법으로 하여 수지 조성물을 제작하고, 실시예 1 과 동일한 시험을 실행한다. 평가결과를 표 1, 표 2 및 표 3 에 나타낸다.According to the formulation of Table 1, Table 2 and Table 3, a resin composition is produced in the same manner as in Example 1, and the same test as in Example 1 is performed. The evaluation results are shown in Table 1, Table 2 and Table 3.
상기 실시예에서 알 수 있는 바와 같이 본 발명의 할로겐계, 삼산화안티몬 등의 난연제를 함유하지 않은 에폭시 수지 조성물로 밀봉된 반도체장치는 난연성 및 내습성이 뛰어나다.As can be seen from the above embodiment, the semiconductor device sealed with the epoxy resin composition containing no flame retardant such as halogen-based or antimony trioxide of the present invention is excellent in flame retardancy and moisture resistance.
Claims (6)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9306847A JPH11140277A (en) | 1997-11-10 | 1997-11-10 | Epoxy resin composition and semiconductor device produced by using the composition |
| JP97-306847 | 1997-11-10 |
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| Publication Number | Publication Date |
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| KR19990044940A KR19990044940A (en) | 1999-06-25 |
| KR100524248B1 true KR100524248B1 (en) | 2005-12-21 |
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|---|---|
| US (1) | US6242110B1 (en) |
| EP (1) | EP0915118B1 (en) |
| JP (1) | JPH11140277A (en) |
| KR (1) | KR100524248B1 (en) |
| DE (1) | DE69821573T2 (en) |
| MY (1) | MY115618A (en) |
| SG (1) | SG87012A1 (en) |
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- 1998-11-03 US US09/184,989 patent/US6242110B1/en not_active Expired - Lifetime
- 1998-11-09 DE DE69821573T patent/DE69821573T2/en not_active Expired - Lifetime
- 1998-11-09 EP EP98121270A patent/EP0915118B1/en not_active Expired - Lifetime
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Also Published As
| Publication number | Publication date |
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| JPH11140277A (en) | 1999-05-25 |
| KR19990044940A (en) | 1999-06-25 |
| EP0915118A1 (en) | 1999-05-12 |
| DE69821573T2 (en) | 2004-12-16 |
| DE69821573D1 (en) | 2004-03-18 |
| SG87012A1 (en) | 2002-03-19 |
| US6242110B1 (en) | 2001-06-05 |
| EP0915118B1 (en) | 2004-02-11 |
| MY115618A (en) | 2003-07-31 |
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